Photochromic element containing surfactant and method for manufacturing same

Abstract

The present invention relates to a surfactant-containing photochromic element and a method for manufacturing the same, and more specifically, to a surfactant-containing photochromic element and a method for manufacturing the same, the surfactant-containing photochromic element being characterized in that the above-mentioned photochromic element contains a surfactant so as to have excellent physical properties and discoloration properties.

Description

Technical Field

[0001] The present invention relates to a photochromic element containing a surfactant and a method for manufacturing the same. More specifically, the photochromic element contains a surfactant, thereby having excellent physical properties and color changing properties.

[0002] The present invention is the result of research conducted from March 1, 2021 to February 29, 2024 with support from the government (Ministry of Science, ICT) and the Korea Research Foundation's project "Application of next-generation highly transparent and highly stretchable sensors and electrochemical display elements using high-performance multifunctional ionic conductive non-ionic conductive polymer gels based on non-aqueous systems" (No. 1711190086). Background Art

[0003] Photochromic substances are compounds that absorb light energy of a specific wavelength to change their molecular structure and change the color that appears to the outside in this state. They have the property of reversibly returning to their previous molecular structure if the energy applied to the substance is interrupted.

[0004] When the photochromic material is composed of inorganic substances such as metal oxides, alkaline earth metals, mercury compounds, and transition metal compounds, it is very stable to external environments such as ultraviolet rays, oxygen, and solvents, but it is very troublesome to process, so there are problems such as difficulty in fully utilizing. On the contrary, organic photochromic dyes such as benzopyran, naphthopyran, spiropyran, spirooxazine, fulgimide, diarylethene, and azo compounds are easily dissolved in solvents or powdered and fully utilized, but become unstable due to light, oxygen, acid, organic solvents, etc., and therefore have problems such as insufficient durability.

[0005] The disadvantage of photochromic dyes is that, as mentioned above, due to external environmental factors, the chemical molecular structure is destroyed, so that it is relatively easy to carry out a side reaction in which the color change of light disappears. It is known that the cause of this side reaction is that the oxidation reaction of free radicals or active oxygen proceeds alone or simultaneously, thereby destroying the dye structure.

[0006] On the other hand, spiropyran is the most common photochromic dye, which has the property of changing color to blue when reacting with UV light, and therefore research is being conducted on adding spiropyran to various polymers.

[0007] In this regard, the most commonly used polymer is polydimethylsiloxane (PDMS). When spiropyran is mixed into the polydimethylsiloxane (PDMS), photochromism can be achieved and flexible components can be manufactured. However, since the polydimethylsiloxane (PDMS) itself has poor elongation, it has been difficult to manufacture stretchable components.

[0008] Therefore, the present inventors have conducted studies to solve the above-mentioned problems and have found that when a surfactant is further included when manufacturing a photochromic element, the photochromic element has not only high flexibility and improved elongation but also excellent color changing properties, thereby completing the present invention.

[0009] In this regard, Korean Patent Publication No. 10-2017-0014594 discloses an organic thin film using a fluorescent conjugated polymer and a photochromic dye, a method for manufacturing the same, and a photoresponsive fluorescent patterning method using the organic thin film. Summary of the invention

[0010] Technical issues

[0011] The present invention provides a method for producing a photochromic element containing a surfactant.

[0012] Furthermore, the present invention provides a photochromic element containing a surfactant.

[0013] Problem Solving Solutions

[0014] As a technical solution aimed at solving the technical problems mentioned above, one aspect of the present invention provides a method for manufacturing a photochromic element, which includes: a step of mixing a polymer resin and a curing agent; a step of adding a photochromic dye to the above mixture; and a step of adding a surfactant to the mixture to which the above photochromic dye is added.

[0015] The polymer resin may include a polymer resin selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane, polyacryl, polyepoxy, polyester, polystyrene (PS), polyacrylate (PA), and combinations thereof.

[0016] The curing agent may include a substance selected from the group consisting of polydimethylsiloxane (PDMS), polyisocyanate, hexamethylene diisocyanate, ethyleneimine, propyleneimine, polyethylene glycol dimethacrylate (Poly (ethylene glycol dimethacrylate) (PEGDMA)), polyethylene glycol diacrylate (Poly (ethylene glycoldiactylate) (PEGDMA)), dicumyl peroxide, dibenzoyl peroxide, tert-Butylcumylperoxide, SYLGARD 184 ELASTOMER CURING AGENT, and combinations thereof.

[0017] The photochromic dye may include a substance selected from the group consisting of spiropyran, spirooxazine, naphthopyran, fulgimide, azobenzene, and combinations thereof.

[0018] The above-mentioned surfactant can include a substance selected from the group consisting of Triton X-100 (trademark name), myristyltrimethylammonium bromide, 3-(N,N-dimethyldodecylammonium) propane sulfonate (N-Dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate), 3-(decyldimethylammonio)propanesulfonate inner salt zwitterionic detergent), 3-sulfopropyl tetradecyldimethylammonium (3-(N,N-dimethylmyristylammonio)propansulfonate), Thesit (registered trademark name), dodecyl-β-D-maltoside (n-Dodecylβ-D-maltoside), octyl-β-D-pyranoglucoside (Octylβ-D-glucopyranoside) and combinations thereof.

[0019] The content of the curing agent may be 1 part by weight to 30 parts by weight relative to 100 parts by weight of the polymer resin.

[0020] The photochromic dye may be contained in an amount of 0.1 to 10 parts by weight relative to 100 parts by weight of the mixture comprising the polymer resin and the curing agent.

[0021] The surfactant may be contained in an amount of 0.01 to 2 parts by weight relative to 100 parts by weight of the mixture comprising the polymer resin and the curing agent.

[0022] In another aspect of the present invention, there is provided a photochromic element comprising a polymer resin, a curing agent, a photochromic dye, and a surfactant.

[0023] The color change of the photochromic element can be completed within 1 minute.

[0024] The photochromic element can be completely decolorized within 10 minutes.

[0025] The photochromic element may show a transmittance of 45% to 75% in light having a wavelength of 593 nm when changing color.

[0026] The photochromic element may show a transmittance of 30% or more different from that before the color change in light with a wavelength of 593 nm when the color change occurs.

[0027] The photochromic element can show a tensile strain of 350% or more based on a tensile strength of 1 MPa.

[0028] In addition, another aspect of the present invention provides an artificial skin comprising the above-mentioned photochromic element.

[0029] Effects of the Invention

[0030] The photochromic element according to the present invention as described above contains a surfactant, thereby being able to improve physical properties such as flexibility and elongation.

[0031] In addition, the photochromic element can have excellent color changing properties and color erasing properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The synthesis process of spiropyran according to one embodiment of the present invention is shown.

[0033] Figure 2 is a graph showing absorbance according to wavelength of a photochromic element according to one embodiment of the present invention.

[0034] Figure 3are photographs showing color change and color loss of a photochromic element according to one example of the present invention.

[0035] Figure 4 is a graph showing the transmittance of a photochromic element according to one embodiment of the present invention.

[0036] Figure 5 A stress-strain curve of a photochromic element according to one embodiment of the present invention is shown. DETAILED DESCRIPTION

[0037] The present invention is further described in detail below. However, the present invention can be implemented in many different ways, and the present invention is not limited to the embodiments described here, but is only defined by the appended claims.

[0038] Subsequently, the terms used in the present invention are only used to illustrate specific embodiments and are not intended to limit the present invention. A single expression includes multiple expressions unless there is a clear difference in meaning in the context. Throughout the specification of the present invention, "comprising" a certain constituent element means that, unless there is a special record to the contrary, other constituent elements may be further included rather than excluded.

[0039] The first aspect of the present application provides a method for manufacturing a photochromic element, which includes: a step of mixing a polymer resin and a curing agent; a step of adding a photochromic dye to the mixture; and a step of adding a surfactant to the mixture with the photochromic dye added.

[0040] Hereinafter, the method for manufacturing the photochromic element according to the first aspect of the present application will be described in detail step by step.

[0041] First, in a specific implementation example of the present application, the method for manufacturing the photochromic element may include a step of mixing a polymer resin and a curing agent.

[0042] In a specific implementation example of the present application, the above-mentioned polymer resin is a substance that serves as the base of the photochromic element, which may include a polymer resin selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane, polyacryl, polyepoxy, polyester, polystyrene (PS), polyacrylate (PA) and combinations thereof. According to one embodiment of the present invention, polydimethylsiloxane (PDMS) can be used.

[0043] At this time, the polydimethylsiloxane (PDMS) may be represented by the following Chemical Formula 1.

[0044] [Chemical formula 1]

[0045]

[0046] In a specific implementation example of the present application, the curing agent may include a substance selected from the group consisting of polydimethylsiloxane (PDMS), polyisocyanate, hexamethylene diisocyanate, ethyleneimine, propyleneimine, polyethylene glycol dimethacrylate (Poly (ethylene glycol dimethacrylate) (PEGDMA)), polyethylene glycol diacrylate (Poly (ethylene glycol diactylate) (PEGDMA)), dicumyl peroxide, dibenzoyl peroxide, tert-Butylcumyl peroxide, SYLGARD 184 ELASTOMER CURING AGENT, and combinations thereof. The type of curing agent is not particularly limited. However, according to an embodiment of the present invention, polydimethylsiloxane curing agent (PDMS curing agent) and SYLGARD 184 curing agent (SYLGARD 184ELASTOMER CURING AGENT).

[0047] In a specific implementation example of the present application, relative to 100 parts by weight of the above-mentioned polymer resin, the content of the above-mentioned curing agent can be 1 part by weight to 30 parts by weight, preferably, can be 5 parts by weight to 15 parts by weight. According to one embodiment of the present invention, it can be approximately 10 parts by weight.

[0048] Next, in a specific implementation example of the present application, the method for manufacturing the photochromic element may include a step of adding a photochromic dye to the mixture.

[0049] In a specific implementation example of the present application, the photochromic dye may include a substance selected from the group consisting of spiropyran, spirooxazine, naphthopyran, fulgimide, azobenzene and a combination thereof. According to one embodiment of the present invention, spiropyran may be used. In this case, the spiropyran may have the property of reacting with UV to turn blue, and may be used Figure 1 On the other hand, the spiropyran can be represented by the following chemical formula 2.

[0050] [Chemical formula 2]

[0051]

[0052] In a specific implementation example of the present application, the content of the photochromic dye can be 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the mixture comprising the polymer resin and the curing agent. According to an embodiment of the present invention, it can be approximately 2 parts by weight. On the other hand, when the content of the photochromic dye is less than 0.1 parts by weight relative to 100 parts by weight of the mixture comprising the polymer resin and the curing agent, the content of the photochromic dye is too small, so the color change performance will decrease. When it exceeds 10 parts by weight, the content of the photochromic dye is too much, so the dispersion stability to the polymer resin will decrease.

[0053] Next, in a specific implementation example of the present application, the method for manufacturing the photochromic element may include a step of adding a surfactant to the mixture to which the photochromic dye is added.

[0054] In a specific implementation example of the present application, the above-mentioned photochromic element can improve physical properties such as flexibility and stretchability due to the further addition of a surfactant.

[0055] In a specific implementation example of the present application, the above-mentioned surfactant may include a substance selected from the group consisting of Triton X-100 (trademark name), myristyltrimethylammonium bromide, 3-(N,N-dimethyldodecylammonium) propane sulfonate (N-Dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate), 3-(decyldimethylammonio) propanesulfonate inner salt zwitterionic detergent), 3-sulfopropyl tetradecyldimethylammonium (3-(N,N-dimethylmyristylammonio) propansulfonate), Thesit (registered trademark name), dodecyl-β-D-maltoside (n-Dodecylβ-D-maltoside), octyl-β-D-pyranoglucoside (Octylβ-D-glucopyranoside) and a combination thereof. According to one embodiment of the present invention, Triton can be used. X-100.

[0056] At this time, the Triton X-100 can be represented by the following Chemical Formula 3.

[0057] [Chemical formula 3]

[0058]

[0059] In a specific implementation example of the present application, the content of the above-mentioned surfactant can be 0.01 to 2 parts by weight, preferably 0.01 to 1 part by weight, and according to one embodiment of the present invention, can be 0.1 to 0.5 parts by weight relative to 100 parts by weight of the mixture containing the above-mentioned polymer resin and the curing agent. At this time, when the content of the above-mentioned surfactant is less than 0.01 parts by weight relative to 100 parts by weight of the mixture containing the above-mentioned polymer resin and the curing agent, the content of the surfactant is too small, so that the improvement effect of the physical properties of the photochromic element will be negligible. When it exceeds 2 parts by weight, it has exceeded the content that shows that the surfactant brings an improvement effect on the physical properties, so it will be uneconomical.

[0060] The second aspect of the present application provides a photochromic element containing a polymer resin, a curing agent, a photochromic dye and a surfactant, and an artificial skin containing the photochromic element.

[0061] Although detailed descriptions of portions overlapping with the first aspect of the present application are omitted, the contents described in the first aspect of the present application are similarly applicable even if the descriptions thereof are omitted in the second aspect.

[0062] Hereinafter, the above-mentioned photochromic element and artificial skin according to the second aspect of the present application will be described in detail.

[0063] In a specific implementation example of the present application, the above-mentioned polymer resin is a substance that serves as the base of the photochromic element, which may include a polymer resin selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane, polyacryl, polyepoxy, polyester, polystyrene (PS), polyacrylate (PA) and combinations thereof. According to one embodiment of the present invention, polydimethylsiloxane (PDMS) can be used.

[0064] In a specific implementation example of the present application, the curing agent may include a substance selected from the group consisting of polydimethylsiloxane (PDMS), polyisocyanate, hexamethylene diisocyanate, ethyleneimine, propyleneimine, polyethylene glycol dimethacrylate (Poly (ethylene glycol dimethacrylate) (PEGDMA)), polyethylene glycol diacrylate (Poly (ethylene glycol diactylate) (PEGDMA)), dicumyl peroxide, dibenzoyl peroxide, tert-Butylcumyl peroxide, SYLGARD 184 ELASTOMER CURING AGENT, and combinations thereof. The type of curing agent is not particularly limited. However, according to an embodiment of the present invention, polydimethylsiloxane curing agent (PDMS curing agent) and SYLGARD 184 curing agent (SYLGARD 184ELASTOMER CURING AGENT).

[0065] In a specific implementation example of the present application, the photochromic dye may include a substance selected from the group consisting of spiropyran, spirooxazine, naphthopyran, fulgimide, azobenzene and a combination thereof. According to one embodiment of the present invention, spiropyran may be used. In this case, the spiropyran may have the property of reacting with UV to turn blue, and may be used Figure 1 Synthesized by the synthetic method shown.

[0066] In a specific implementation example of the present application, the above-mentioned surfactant may include a substance selected from the group consisting of Triton X-100 (trademark name), myristyltrimethylammonium bromide, 3-(N,N-dimethyldodecylammonium) propane sulfonate (N-Dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate), 3-(decyldimethylammonio) propanesulfonate inner salt zwitterionic detergent), 3-sulfopropyl tetradecyldimethylammonium (3-(N,N-dimethylmyristylammonio) propansulfonate), Thesit (registered trademark name), dodecyl-β-D-maltoside (n-Dodecylβ-D-maltoside), octyl-β-D-pyranoglucoside (Octylβ-D-glucopyranoside) and a combination thereof. According to one embodiment of the present invention, Triton can be used. X-100.

[0067] In a specific implementation example of the present application, the content of the curing agent can be 1 to 30 parts by weight, preferably 5 to 15 parts by weight, and about 10 parts by weight, relative to 100 parts by weight of the polymer resin. In addition, the content of the photochromic dye can be 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and about 2 parts by weight, relative to 100 parts by weight of the total weight of the polymer resin and the curing agent. On the other hand, when the content of the photochromic dye is less than 0.1 parts by weight relative to 100 parts by weight of the mixture containing the polymer resin and the curing agent, the content of the photochromic dye is too small, so that the color change performance will decrease. When it exceeds 10 parts by weight, the content of the photochromic dye is too much, so that the dispersion stability to the polymer resin will decrease. Furthermore, the content of the surfactant may be 0.01 to 2 parts by weight, preferably 0.01 to 1 part by weight, and according to one embodiment of the present invention, 0.1 to 0.5 parts by weight, relative to 100 parts by weight of the total weight of the polymer resin and the curing agent. At this time, when the content of the surfactant is less than 0.01 parts by weight relative to 100 parts by weight of the mixture containing the polymer resin and the curing agent, the content of the surfactant is too small, and the effect of improving the physical properties of the photochromic element will be negligible. When it exceeds 2 parts by weight, it has exceeded the content that shows that the surfactant brings an improvement effect on the physical properties, so it is not economical.

[0068] In a specific implementation example of the present application, the photochromic element can change color within 1 minute, and can fade within 10 minutes. Preferably, the color change can be completed within approximately 30 seconds, and the color fading can be completed within approximately 5 minutes. In this case, the color change can be completed when UV is irradiated, and the color fading can be completed when UV irradiation is turned off.

[0069] In a specific implementation example of the present application, the photochromic element can show a transmittance of 45% to 75% in light with a wavelength of 593nm when changing color, and the transmittance can decrease as the UV irradiation time passes. On the other hand, the photochromic element can show a transmittance of more than 30% in light with a wavelength of 593nm when changing color than before the color change, and preferably, can show a transmittance of more than 50%.

[0070] In a specific implementation example of the present application, the photochromic element can show a tensile strain of 350% or more based on a tensile strength of 1 MPa. That is, the photochromic element according to the present invention can have excellent physical properties as described above because it further contains a surfactant, and can be used as artificial skin because it has excellent flexibility and elasticity.

[0071] The following describes the embodiments of the present invention in detail so that those skilled in the art can easily implement the present invention. However, the present invention can be implemented in various different ways and is not limited to the embodiments described here.

[0072] Example 1. Preparation of Photochromic Element (Triton X 0.1 wt%)

[0073] First, polydimethylsiloxane (PDMS) and a polydimethylsiloxane curing agent (PDMS curing agent) SYLGARD 184 ELASTOMER CURING AGENT as a curing agent were mixed at a weight ratio of 10:1.

[0074] Afterwards, 2 wt% of Figure 1 To improve the physical properties, only 0.1 wt % of Triton X-100 as a surfactant was added to the spiropyran synthesized by the method, thereby producing a photochromic element in the form of a gel.

[0075] Example 2. Preparation of Photochromic Element (Triton X 0.3 wt %)

[0076] A photochromic element was produced in the same manner as in Example 1 except that the content of Triton X-100 as the surfactant in Example 1 was changed to 0.3 wt %.

[0077] Example 3. Preparation of Photochromic Element (Triton X 0.5 wt%)

[0078] A photochromic element was produced in the same manner as in Example 1 except that the content of Triton X-100 as the surfactant in Example 1 was changed to 0.5 wt %.

[0079] Comparative Example. Preparation of Photochromic Element (Triton X 0wt%)

[0080] A photochromic element was produced in the same manner as in Example 1 except that Triton X-100 as a surfactant was not added.

[0081] Experimental Example 1. Measurement of color change performance of photochromic element

[0082] The UV absorbance of the photochromic element produced in Example 1 was measured, and the results are shown in FIG. Figure 2 middle.

[0083] like Figure 2 As shown, a high absorbance is shown at 593 nm. Figure 3 It can also be confirmed that the photochromic element changes to blue as shown. Figure 3 As shown, it can be confirmed that the photochromic element manufactured according to Example 1 completed the color change in only 30 seconds and then completed the color elimination in only 5 minutes.

[0084] In addition, the transmittance of the photochromic element manufactured in Example 1 was measured over time, and the results are shown in FIG. Figure 4 middle.

[0085] like Figure 4 As shown, the photochromic element showed a transmittance change of 53% or more at the time point of 30 seconds after UV irradiation, and it was confirmed that the photochromic element changed color and became transparent only 5 minutes after UV irradiation was stopped.

[0086] Experimental Example 2. Measurement of physical properties of photochromic elements

[0087] The physical properties of the photochromic elements manufactured in Examples 1 to 3 and Comparative Examples were measured using UTM. The results are shown in FIG. Figure 5 (stress-strain curve).

[0088] like Figure 5 As shown, it can be confirmed that the photochromic element manufactured according to the example of the present invention has a tensile strength that is 3 times lower and a tensile strain that is 2 times lower than that of the photochromic element manufactured according to the comparative example.

[0089] It can be confirmed that the photochromic element manufactured according to the embodiment of the present invention has flexibility and stretchability suitable for artificial skin.

[0090] Although the preferred embodiments and the present invention have been described in detail above with reference to the accompanying drawings, the scope of the technical concept of the present invention is not limited to these drawings and embodiments. Therefore, there are various modifications or embodiments with equivalent scope within the scope of the technical concept of the present invention. Therefore, the scope of rights according to the technical concept of the present invention should be interpreted by the claims, and the technical concept within the scope equivalent to or equivalent to the technical concept should be interpreted as belonging to the scope of rights of the present invention.

Claims

1. A method for manufacturing a photochromic element, characterized in that: include: The step of mixing the polymer resin and the curing agent; The step of adding a photochromic dye to the mixture; as well as, A step of adding a surfactant to the mixture to which the photochromic dye is added.

2. The method for manufacturing a photochromic element according to claim 1, characterized in that: The polymer resin includes a polymer resin selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane, polyacrylic resin, polyepoxy resin, polyester, polystyrene (PS), polyacrylate (PA) and a combination thereof.

3. The method for manufacturing a photochromic element according to claim 1, wherein: The curing agent includes a substance selected from the group consisting of polydimethylsiloxane (PDMS), polyisocyanate, hexamethylene diisocyanate, ethyleneimine, propyleneimine, polyethylene glycol dimethacrylate (PEGDMA), polyethylene glycol diacrylate (PEGDMA), dicumyl peroxide, dibenzoyl peroxide, tert-Butylcumyl peroxide, SYLGARD 184 ELASTOMER CURING AGENT, and combinations thereof.

4. The method for manufacturing a photochromic element according to claim 1, wherein: The photochromic dye includes a substance selected from the group consisting of spiropyran, spirooxazine, naphthopyran, fulgimide, azobenzene and a combination thereof.

5. The method for manufacturing a photochromic element according to claim 1, wherein: The surfactant comprises a substance selected from the group consisting of Triton X-100 (trademark), myristyltrimethylammonium bromide, 3-(N,N-dimethyldodecylammonium) propane sulfonate, 3-(decyldimethylammonio)propanesulfonate inner salt zwitterionic detergent, 3-(N,N-dimethylmyristylammonio)propansulfonate, Thesit (registered trademark), n-Dodecylβ-D-maltoside, Octylβ-D-glucopyranoside and combinations thereof.

6. The method for manufacturing a photochromic element according to claim 1, wherein: The content of the curing agent is 1 part by weight to 30 parts by weight relative to 100 parts by weight of the polymer resin.

7. The method for manufacturing a photochromic element according to claim 1, wherein: The content of the photochromic dye is 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the mixture including the polymer resin and the curing agent.

8. The method for manufacturing a photochromic element according to claim 1, wherein: The content of the surfactant is 0.01 to 2 parts by weight relative to 100 parts by weight of the mixture including the polymer resin and the curing agent.

9. A photochromic element, characterized in that: Contains polymer resin, curing agent, photochromic dye and surfactant.

10. The photochromic element according to claim 9, characterized in that: The color change of the photochromic element is completed within 1 minute.

11. The photochromic element according to claim 9, characterized in that: The photochromic element is completely decolorized within 10 minutes.

12. The photochromic element according to claim 9, characterized in that: The photochromic element shows a transmittance of 45% to 75% in light having a wavelength of 593 nm when changing color.

13. The photochromic element according to claim 9, characterized in that: The photochromic element shows a transmittance (transmittance) of 30% or more changed in light with a wavelength of 593 nm when the color is changed compared with that before the color is changed.

14. The photochromic element according to claim 9, characterized in that: The photochromic element exhibits a tensile strain of 350% or more based on a tensile strength of 1 MPa.

15. An artificial skin, characterized in that: The photochromic element according to claim 9 is included.

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